of basel



riunnnrcn FELIX, or BASEL,

Patented Mar. 8 1932 rivnns'rzaY n BASLE; or. BASED}, SWITZERLAND AZO-DIYESTUEFS AHD} PROCESS OF MAKING SAME.

No Drawing. Application filed October 15, 1929,.Serial no. 400,1 9, and in Switzerland"November*2;'.1928.

Ihe present inventionrelates to the manufacture of am-dyestuffs which are valuable for, among other purposes, dyeing colloids of the cellulose series. It comprises the process of making these dyestuffs, the new'dye stuffs, and the material dyed with the new dyestuffs. 1 7 According to the invention, dyestuffs which are specially suitable for Y coloring lacquers or varnishes or estersgor ethers of cellulose, for instance Zapon varnish or. acetate silk, are-inade by. coupling diazotized esters of nu'cleally not sulfonated ortho -.am-

inophenols with jnucleally notsulfonated aromatic compounds which contain an ,R-H V residue. (RE standing for'Q or N- g, wherein y stands for the o-methane sulfonic acid residue)", and bytreatin'g the. dyestuffs thus obtainedwith sapo-nifying agentsfor-thetpur- :pose of saponifying the ester'and-otherasaponifiable residues present,"i f any, 1 and then,

for the purpose of enhancing-the;fastness properties of the saponified dyestuffs; re--' placing the hydrogen atom of the above mentioned R-H residu'eby an aliphatic residue containing at the most three .carbon atoms.

v This can be done by alkylation; foreXample with methyl chloride; ethyl bromide; ethylene chlorhydrine, epichlo'rhydrine'; ates, or by acidylatiomfor example-with formic acid,

acetic anhydride, propionic acid chloride, and the like. By this operation; the-"OH- V of the diazotizing component standing 7 group in ortho-position to the azo-bridge remains unchanged due 'to'the azo-groupapparently exercising apltotective action. H

Similar products: are also obtained by choosing as coupling component compounds such as dialkylamhne, and then, afterthe 1 coupling is complete, merely treating th'e reaction mixture with saponifyinga'gents. a

The dyestuffs thus obtained apparently correspond with the following generallfor-v mula:

wherein m is an OH- or an NH -group -in; 'which at leastone of the hydrogen atoms is substituted by an alkylresidueor by anacidyl mulaz residue, both-containing at most three canbon atoms. The dyestuffs are yellow to redpowders andd-ye the-aforesaid materials fast yellow to orange and red tints. They may be converted by treatment with .agentsyielding metals fintozmetalliferous" dyestuffs of' which the dyeinggtints may be essentially different from those of the dyestuffs not contam-ing metal and having besides improved propertieslof fastness. 9

V The following examples illustrate the invention, the parts beingbyweighta- Example 1 I I 263 parts of 'paratoluenesulfonic acid ester. of ortho-aminophenol are diazotized and; the dia'z'o-compound thus obtained of the'for sodium I.aniline-wsmethane-sulfonate1 containing 200' parts: offsodium acetate; The dye H GEN-Glam i a can be isolated by: distilling the alcohol, suspending the residue 'inwater, washing-and drying;v ItI iS a yellow" powderifwhichiidislow.

' 213 partsof'the heated with 102 parts of acetic' anhydride for about 4-110mm 100 C. The mass which l solidifies on cooling; is. comminuted and washed withwatenanddried. Thenew dyestuff, which is a yellowpowder, dissolvesv in concentrated sulfuric acid to a yellow-orange solution and dyes acetate silk I fast green yelsolves in concentrated sulfuric acid to a brown:red solution. dyesacetate siljk yel-v Q dyestufi'thus obtained are I stuff which forms quickly, isfiltered; suspendi 'ed in 100 part'sof alcoholand the whole'is Y boiledwith 300 parts'ofcaustic soda solution of 30 per centistreng'thjin a reflux apparatus I for about hounfThe saponifieddye'stuff 'of'the'formulazf a I;

. fonic* acids meta-toluidine, V para-xylidine,

-UN= ONHcHLsom low. It corresponds Very probably with the formula:

and is made according to the following equations:

By alkylation of the saponified dyestuif of the first paragraph of this example with ethylchloride there may be obtained a product of the formula: V

which dyes acetate silk orange tints which are fast to light and are not phototropic. This later product is also obtained by coupling the diazotized para-toluene-sulfonic acid ester of o-aminophenol with diethylaniline and saponification of the dyestuft'.

Similar products are obtained when for the m-methanesulfonic acid of aniline, that,

of ortho-toluidine or ortho-anisidine is substituted; or instead of these w-methanesul- E mample 2 263 parts of the para-toluenesulfonic acid ester of ortho-aminophenol are diazotized and introduced into a solution of 116 parts of sodium phenolate alkaline with sodium carbonate. The dyestuff of the formula which is immediately formed is filtered and suspended in 1000 parts of alcohol; the suspensionis mixed with 150 parts of caustic soda solution of 30 per centstrength and the whole is boiled for a 4 hour in a reflux apparatus. By distilling the alcohol, taking up the residue in water, filtering and washing, the saponified dyestufi' of the formula:

is obtained in the form of a yellow powder 0-SOrOCH3 which dissolves in concentrated sulfuric acid to a'brown red solution. ,j v42 parts of the dyestuff thus obtained are dissolved in 20 parts of caustic soda solution of 30 per cent. strength and 200 parts of alcohol. The solution is mixed with 20 parts of ethyl chloride and the whole is heated in r a closed vessel for 5 hours at -95 C.. After cooling, the dyestuif which has separated is filtered and washed. It is a yellow'powder, soluble in concentrated sulfuric acid to a yellow brown solution. It dyes acetate silk green-yellow. It corresponds very probably with the formula:

and is produced according to the following equations:

cation Similar products are obtained when there 1s substituted for the phenol another compound containing a hydroxyl-group, such as 7533 ortho-cresol, meta-cresol, meta-chlorophenol, or a naphthol; andwhen for the ortho-aininophenol there is substituted a substitution product thereof, such as the 5-nitro-ortho-aminophenol or 5-chloroi th pling components are used. Varnishes and acetate silk are dyed, for example, yellow to orange and red. tints by means of the unsaponified azo-dyestufl's from dimethylor div v cessively, with caustic alkali-es, and with acetic anhydride.

ethyl-aniline, ,B-naphthol, 213- or 1:4-hydroxynaphthoicacid ester, ,B-naphthylamine,

ethyl-,G-naphthylamine or the like. 7 Q

What I claim is 1. Process for the manufacture ofazo-dyestuffs, consisting in coupling diazotized esters of nucleally not sulfonated ortho-amino-phenols with such nucleally not Sulionatedaromatic compounds of the benzene series which I contain an RH residue, B being 0 or N 1 wherein z stands for the o-methane sulfonic acid residue, treating the products thus ob tained with caustic alkalies, and then replacing the hydrogenatom of the above mentionedR H residue by an aliphatic residue containing at the most three carbon atoms.

2. Processfor the manufacture oiazo-dye- I stufis, consisting in coupling diazotized esters of nucleally not sulfonated ortho-amino-phenols with such nucleally not sulfonated aromatic compounds of the benzene series which contain an lt-H residue, R being 0 or Ny,

:wherein y stands for thew-methane sulfonic acid residue, in paraposition to the place of coupling, treating the products thus obtained with caustic alkalies, and then replacingthe products thus obtain-ed with caustic alkalies,

and then replacing at least one of the hydrogen atoms of the formed NH -group by an aliphatic residue containing at the most three carbon atoms. i

4. Process for the manufacture of azo-dyestufis, consisting in coupling diazotized esters of nucleally not'sulfonatedortho-amino-phenols with such nucleally not sulfonated aro-,

matic compounds of the benzene series which contain an NH-y group, g' 'standing for the (ii-methane sulfonic acid "residue in para-position to v the place of coupling, treating the products thus obtained with caustic alkalies,

and then acidylating with acidylating agents deriving from such aliphatic carboxylic acids which contain not more than three, carbon atoms. v I a 5Proc essforthe manufacturedazo dye stufis, consisting in couplingcantata-a ters'of nucleally. not sulfonated ortho-amino phenols withsuch nucleallylnot sulfonated,

aromatic compounds'ot the benzene series for the w-methane sulfonic acid,residuewin then treatingthe products thus obtained suc 6. Process for the Inanufactureiof azo-dye stuiis, consisting n .couplingidia'zotized es- .para-pos'ition'to the placeof cou'pling,. and

ters, of ortho-amino-phenol with wemethanersul-if onic acids ofgcompoiinds the general formula: 1- H wherein R is alkyl or O -alliyl, and then treat- Process for the manufacture of an azo- 'dyest'u'fl', consisting in i coupling; diazoti'zed estersofortho aininophenol with the (a-me? "than u1 nie f'a'cid; of ""ortho-toluidine,: and then treating thei'product' thus obtainedf'suc ces'sivelywith'caustic alkalie's", and with acetic anhy r de- 7 is new products formula: f I ions:

the azoidyestutls of the alkali es, and with "acetic 'anhywherein the position standing in para-posi- 7 tion to the OH-group is unsubstituted, aryl; stands for a nucleus of the'benzene series,

and m is a nitrogen or oxygen atom which, on the one hand, is bound by'one valency to the aryl'nucleus, and, on the other hand, at least once to a group containing at most three.-

carbon atoms, which products'form yellow to red powder-s dissolving in organic solvents to yellow or orange solutions. V

9 As new productsthe azo-dyestufis of the general formula:

m is a nitrogen or oxygen atom which, on the one hand, is bound by one valency to the) aryl nucleus,iand, on the otherv hand, atleast once to a group containing at most three car- I bon atoms, which products form yellow to red powders dissolving in organic solvents to yellow to orange solutions.

which contain an NI-I-y. group, y'standing V I 10, new products the azo-dyestuifs of the general formula:

wherein the position standing in para-position to the OH-group is unsubstituted, aryl stands for a nucleus of the benzene series, B stands for H or an organic residue consisting of at most 3 carbon atoms, and R for anorganic residue consisting of at most 3 carbon atoms, which products form yellow to orange powders, dissolving in organic solvents-to solutions of similar color, yielding on acetate silk yellow to orange not phototropic tints.

11. As new products the azo-dyestuifs of the general formula:

wherein the arylrresidue originating from ortho-aminophenol is unsubstituted, and

wherein R stands for alkyl or O-alkyl, which products form yellow powders, dissolving in organic solvents to yellow solutions, and, dyeing acetate silk yellow tints.

In witness whereof I have hereunto signed my name this 4th day of October, 1929.

FRIEDRICH FELIX. 

